Calcium-phosphate nanofiber matrices comprising randomly dispersed crystalline calcium-phosphate nanofibers are provided. The nanofibers are synthesized using sol-gel methods combined with electrospinning. The nanofibers may be hollow, solid or may comprise a calcium-phosphate shell surrounding a polymer containing inner core to which biologically functional additives may be added. The nanofiber matrices may be used to culture bone and dental cells, and as implants to treat bone, dental or periodontal diseases and defects.